CN105694702A - Single-component moisture-curable organic silicon modified polyurethane waterproof paint and preparation method - Google Patents
Single-component moisture-curable organic silicon modified polyurethane waterproof paint and preparation method Download PDFInfo
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- CN105694702A CN105694702A CN201610148015.1A CN201610148015A CN105694702A CN 105694702 A CN105694702 A CN 105694702A CN 201610148015 A CN201610148015 A CN 201610148015A CN 105694702 A CN105694702 A CN 105694702A
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Abstract
The invention belongs to the field of polyurethane waterproof paint and discloses single-component moisture-curable organic silicon modified polyurethane waterproof paint and a preparation method. The single-component moisture-curable organic silicon modified polyurethane waterproof paint is prepared from, by weight, 100 parts of organic silicon modified polyurethane prepolymer, 5-50 parts of filler, 10-30 parts of plasticizer and 0.5-5 parts of a foaming agent. The invention further provides a preparation method of the organic silicon modified polyurethane prepolymer. The components of the paint are dispersed for 1-2 h at room temperature at high speed and evenly stirred, and the single-component moisture-curable organic silicon modified polyurethane waterproof paint is obtained. The prepared polyurethane waterproof paint is of a single-component moisture-curable type, is simple in construction technology, and does not contain organic volatile matter, TDI and other toxic isocyanate monomers. The environment-friendly polyurethane waterproof paint is excellent in waterproof performance and weather resistance and has long-time antifouling capability.
Description
Technical field
The invention belongs to polyurethane water-proof paint field, particularly to a kind of mono component wet solidifying organic silicon modified polyurethane water-repellent paint and preparation method thereof。
Background technology
Polyurethane water-proof paint is a kind of water-repellent paint being main film forming substance with polyurethane, there is because of it features such as the caking property of excellence, mechanical property, anti-wear performance, ageing-resistant performance, be widely used in the waterproofing work in the Architectural Equipment fields such as building inside and outside wall, road, bridge。At present, polyurethane water-proof paint mainly has asphalt polyurethane water-proof paint, single-component polyurethane water-proof paint, double-composition polyurethane waterproof paint, aqueous polyurethane water-repellent paint spray polyurea elastomer water-repellent paint, color waterproof polyurethane paint etc.。Wherein wet-solidifying single-component polyurethane coating is by reacting and film-forming with the dampness in air with the-NCO performed polymer being end group。Due to performed polymer moderate viscosity, because of without with organic solvent diluting, it can within relative humidity 90% when construction。Therefore monocomponent moisture cure water-repellent paint easy construction, nuisanceless, be conducive to environmental protection, reasonable price, be the developing direction of polyurethane water-proof paint。But single-component polyurethane water-proof paint usually makes base stock with TDI, MDI and polyethers, weatherability is excessively poor, easily aoxidize under action of ultraviolet radiation, cause the shortcomings such as film flavescence, efflorescence, currently for this problem mainly by adding UV absorbent and antioxidant, improve its weather resistance, but can not fundamentally change the performance of material。
Organosilicon has resistant of high or low temperature, weatherability, resistance to oxidation stability, the premium properties such as corrosion-resistant, therefore, can effectively improve the waterproof of coating, antifouling capacity with organic silicon modified polyurethane water-repellent paint。And, current organic silicon modified polyurethane water-repellent paint is broadly divided into physical modification and chemical modification。The organosilicon of physical modification slowly precipitates out in the use procedure of coating so that the water-proof stain-resistant ability of coating surface gradually reduces。Organosilicon is linked in the main chain of polyurethane by organosilicon chemistry modified polyurethane water-repellent paint often, although the long-lasting of organic silicon modified polyurethane coating water-proof stain-resistant can be effectively improved, but the motion of the silicone segments owing to being positioned on main chain is subject to certain restrictions, easily it is embedded in the inside of coating, and do not reach the surface of coating, make modified effect be substantially reduced。
Summary of the invention
In order to overcome shortcoming and the deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is in that to provide a kind of mono component wet solidifying organic silicon modified polyurethane water-repellent paint。
Another object of the present invention is in that the preparation method providing a kind of above-mentioned mono component wet solidifying organic silicon modified polyurethane water-repellent paint。
The purpose of the present invention is realized by following proposal:
A kind of mono component wet solidifying organic silicon modified polyurethane water-repellent paint, specifically includes the following component according to weight portion:
The preparation method of described organic silicon modified polyurethane prepolymer is as follows: according to weight ratio, (1) by 100 parts of monohydroxy polydimethylsiloxane, 5～30 parts of diisocyanate are blended under catalyst action at 50～100 DEG C and react 0.5～5h, add 10～40 parts of trimethylolpropanes, continue reaction 1～3h, prepare the chain extender containing organosilicon long-chain；(2) by 50～100 parts of PEPA/polyether polyol, 5～50 parts of isocyanate-monomers react 5～10h at 50～100 DEG C, add the chain extender that 5～25 parts of steps (1) prepare at 50～100 DEG C, react 3～5h, namely can obtain organic silicon modified polyurethane prepolymer。
In the preparation method of described organic silicon modified polyurethane prepolymer, the mol ratio of the isocyanate group that the amount of monohydroxy polydimethylsiloxane used and diisocyanate is preferably the hydroxyl according to monohydroxy polydimethylsiloxane and diisocyanate is 1:1。
In the preparation method of described organic silicon modified polyurethane prepolymer, described catalyst is organic tin catalyst, such as dibutyl tin dilaurate, Dibutyltin oxide etc.。
In the preparation method of described organic silicon modified polyurethane prepolymer, described isocyanates be toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate, 4,4-methyl diphenylene diisocyanate and 1, at least one in hexamethylene-diisocyanate etc.。
In the preparation method of described organic silicon modified polyurethane prepolymer, it is 2 that described PEPA is preferably average functionality, and at least one in para Toluic Acid's PEPA, toluene PEPA, succinic acid PEPA, polycaprolactone polyol and decanedioic acid PEPA etc. that molecular weight is 1500～6000, more preferably para Toluic Acid's PEPA and at least one in toluene PEPA。
In the preparation method of described organic silicon modified polyurethane prepolymer, described polyether polyol is preferably at least one in Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol and PTMG etc.。
In the mono component wet solidifying organic silicon modified polyurethane water-repellent paint of the present invention, described filler is preferably at least one in silicon dioxide, zinc oxide, titanium oxide, Kaolin, Pulvis Talci, mica powder, calcium carbonate and montmorillonite。
In the mono component wet solidifying organic silicon modified polyurethane water-repellent paint of the present invention, described plasticizer is preferably at least one in chlorinated paraffin, o-phthalic acid dibutyl ester and dibutyl phthalate。
In the mono component wet solidifying organic silicon modified polyurethane water-repellent paint of the present invention, described defoamer is preferably at least one in BYK055, BYK066N, BEK760, DF-879, TEGOfoamexK3, calcium oxide, calcium hydroxide and Lithium hydrate etc.。
The mono component wet solidifying organic silicon modified polyurethane water-repellent paint of the present invention can also include 0～10 weight portion pigment, 0～0.5 weight portion levelling agent, 0～0.5 weight portion wetting agent, 0～0.5 parts per weight dispersing agent and 0～0.5 weight portion antifreeze。
Described pigment can be at least one in the inorganic pigments such as Degussa white carbon black, iron oxide red and iron oxide yellow。
Described levelling agent can be at least one in esters of acrylic acid levelling agent, polydimethylsiloxane class levelling agent and polyether-modified polydimethylsiloxane class levelling agent。
Described wetting agent can be at least one in TEGO450, BYK346, Silok8040 and K-LS315。
Described dispersant can be at least one in BYK-P104, BYK-P105 and BYK-163。
Described antifreeze can be at least one in propylene glycol, ethylene glycol, ethanol and methanol。
Polyurethane water-proof paint prepared by the present invention is mono component wet solidifying type, there is construction technology simple, without the poisonous isocyanate-monomer such as organic volatile, TDI, be a kind of water resistance with excellence, weatherability, the polyurethane water-proof paint of the environmental protection of long-term antifouling property。
The preparation method that the present invention also provides for a kind of above-mentioned mono component wet solidifying organic silicon modified polyurethane water-repellent paint, comprise the steps: 100 weight portion organic silicon modified polyurethane prepolymers, 5～50 parts of filler material by weight, 10～30 parts by weight of plasticizer, 0.5～5 weight portion defoamer mixing, it is uniformly dispersed, obtains the mono component wet solidifying organic silicon modified polyurethane water-repellent paint of the present invention。
The described preferred high speed dispersion 1～2h that is uniformly dispersed。
Described component is preferably added respectively, adds and adds lower one after one stirs again。
The mechanism of the present invention is:
The present invention utilizes diisocyanate that prepared by monohydroxy polysiloxanes and trimethylolpropane polyurethane chain extender, by long chain silicone being incorporated in the side chain of urethane acrylate in the process prepare polyurethane acrylate prepolymer, when making to solidify under the effect of single-component polyurethane water-proof paint dampness in atmosphere by long side chain organosilicon rivet clasp in the cross-linked network structure of coating, the flexible chain of the polysiloxanes segment owing to having excellent weather resistance is longer, easily float to the surface of coating, prepared organic silicon modified polyurethane water-repellent paint is made to have the ageing-resistant performance of excellence and long-term water-fast, the performance such as antifouling。
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) present invention utilizes diisocyanate that prepared by monohydroxy polysiloxanes and trimethylolpropane polyurethane chain extender, long chain silicone is incorporated in the side chain of polyurethane, solidify in the cross-linked network structure by fixing for long side chain organosilicon polyurethane water-proof paint by coating, the effective ageing-resistant performance improving polyurethane water-proof paint and the long-term performance such as water-fast, antifouling。
(2) in the water-repellent paint of polyurethane, introduce the polysiloxanes segment with excellent weather resistance and can effectively improve the weatherability of polyurethane water-proof paint。
(3) by the solidification process of water-repellent paint, by polysiloxanes segment one end rivet clasp in coating, owing to the flexible chain of polysiloxanes is longer, it is easy to float to the surface of coating, it is possible to be effectively improved the performance such as water-fast, antifouling that coating is long-term under relatively low silicone content。
(4) this polyurethane water-proof paint is mono component wet solidifying type, is used without metering, it is not necessary to add firming agent, and without poisonous isocyanate-monomers such as TDI, use procedure non-volatility solvent exists, and has the performance of environmental protection。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this。
Embodiment 1
(1) according to weight ratio, by the monohydroxy polydimethylsiloxane of 100 parts, 8.5 parts of toluene di-isocyanate(TDI)s join and react 3h in reaction vessel under the catalytic action of dibutyl tin dilaurate at 80 DEG C, then 10 parts of trimethylolpropanes are added, continue reaction 1.5h, prepare the chain extender containing organosilicon long-chain。
(2) according to weight ratio, in the reactor equipped with stirring and temperature regulating device, it is sequentially added into 25 parts of para Toluic Acid's dibutyl ester dihydroxylic alcohols, 25 parts of Polyethylene Glycol dihydroxylic alcohols, 10 parts of toluene diisocyanate monomer react 10h at 50 DEG C, it is subsequently adding 5 parts of chain extenders prepared in (1) at 60 DEG C, reacts 4h, namely can obtain organic silicon modified polyurethane prepolymer product。
(3) according to weight ratio, by 100 parts of organic silicon modified polyurethane prepolymers, 15 parts of o-phthalic acid dibutyl esters, 0.3 part of Siloxane-Oxyalkylene Copolymers levelling agent, 0.1 part of TEG0450, 0.1 part of silox8040, 0.03 part of dispersant B YK-P104, 0.03 part of dispersant B YK-P105, 0.1 part of defoamer BYK055, 0.4 part of calcium oxide, 0.1 part of propylene glycol, 0.4 part of methanol, 10 parts of zinc oxide, 15 parts of titanium oxides, 15 parts of mica powders, 1 part of Degussa white carbon black is added sequentially in reaction vessel, often add a kind of raw material, after stirring, add another raw material, high speed dispersion 1h under room temperature, namely organic silicon modified polyurethane water-repellent paint can be obtained after stirring。
Embodiment 2
(1) according to weight ratio, by the monohydroxy polydimethylsiloxane of 100 parts, 3 parts of toluene di-isocyanate(TDI)s, 2 parts of isophorone diisocyanate join reacts 5h under the catalytic action of Dibutyltin oxide at 50 DEG C in reaction vessel, then 10 parts of trimethylolpropanes are added, continue reaction 3h, prepare the chain extender containing organosilicon long-chain。
(2) according to weight ratio, in the reactor equipped with stirring and temperature regulating device, it is sequentially added into 30 parts of poly-succinic two hexanol dihydroxylic alcohols, 30 parts of polytetramethylene glycol dihydroxylic alcohols, 5 parts of isophorone diisocyanate monomers react 8h at 80 DEG C, it is subsequently adding 10 parts of chain extenders prepared in (1) at 50 DEG C, reacts 3h, namely can obtain organic silicon modified polyurethane prepolymer product。
(3) according to weight ratio, by 100 parts of organic silicon modified polyurethane prepolymers, 5 parts of dibutyl phthalates, 5 parts of chlorinated paraffins, 0.01 part of polydimethylsiloxane levelling agent, 0.05 part of wetting agent L-LS315, 0.1 part of dispersant B YK-163, 0.2 part of dispersant B YK-105, 0.2 part of defoamer BYK066N, 0.3 part of defoamer BEK760, 4.5 parts of calcium hydroxide, 10 parts of calcium carbonate, 5 parts of iron oxide red .1 part iron oxide yellows are added sequentially in reaction vessel, often add a kind of raw material, after stirring, add another raw material, high speed dispersion 2h under room temperature, both organic silicon modified polyurethane water-repellent paint can have been obtained after stirring。
Embodiment 3
(1) according to weight ratio, by the monohydroxy polydimethylsiloxane of 100 parts, 20 parts of toluene di-isocyanate(TDI)s, 5 part 4,4-methyl diphenylene diisocyanate joins and reacts 4h in reaction vessel under the catalytic action of dibutyl tin dilaurate at 60 DEG C, then add 30 parts of trimethylolpropanes, continue reaction 2h, prepare the chain extender containing organosilicon long-chain。
(2) according to weight ratio, in the reactor equipped with stirring and temperature regulating device, it is sequentially added into 100 parts of polycaprolactone diolss, 15 part 1, hexamethylene-diisocyanate, 5 parts of toluene diisocyanate monomer react 5h at 60 DEG C, are subsequently adding 25 parts of chain extenders prepared in (1) and react 3h at 80 DEG C, namely can obtain organic silicon modified polyurethane prepolymer product。
(3) according to weight ratio, by 100 parts of organic silicon modified polyurethane prepolymers, 15 parts of dibutyl phthalates, 15 o-phthalic acid dibutyl esters, 0.4 part of esters of acrylic acid levelling agent, 0.1 part of polydimethylsiloxane class levelling agent, 0.01 part of wetting agent BYK346, 0.1 part of defoamer DF-879, 3 parts of Lithium hydrates, 0.03 part of ethanol, 0.02 part of propylene glycol, 5 parts of silicon dioxide, 5 parts of titanium dioxide, 5 parts of mica powders, 10 parts of calcium carbonate, 5 parts of montmorillonites, 8 parts of Degussa white carbon blacks are added sequentially in reaction vessel, often add a kind of raw material, after stirring, add another raw material, high speed dispersion 1.2h under room temperature, both organic silicon modified polyurethane water-repellent paint can have been obtained after stirring。
Embodiment 4
(1) according to weight ratio, by 100 parts of monohydroxy polydimethylsiloxane, 5 parts of toluene di-isocyanate(TDI)s, 5 parts of hexamethylene diisocyanates join and react 0.5h in reaction vessel under the catalytic action of Dibutyltin oxide at 100 DEG C, then 25 parts of trimethylolpropanes are added, continue reaction 1h, prepare the chain extender containing organosilicon long-chain。
(2) according to weight ratio, in the reactor equipped with stirring and temperature regulating device, it is sequentially added into 50 parts of poly-decanedioic acid two butyl alcohol ester dihydroxylic alcohols, 30 parts to polyphenyl formic acid two alcohol ester dihydroxylic alcohols, 20 parts of polypropylene glycol diols, 15 parts of isocyanate-monomers react 5h at 100 DEG C, are subsequently adding 15 parts of chain extenders prepared in (1) and react 5h at 100 DEG C, namely can obtain organic silicon modified polyurethane prepolymer product。
(3) according to weight ratio, by 100 parts of organic silicon modified polyurethane prepolymers, 20 parts of dioctyl phthalates, 6 parts of chlorinated paraffins, 0.05 part of polyether-modified polydimethylsiloxane levelling agent, 0.1 part of dispersant B YK104, 0.2 part of dispersant B YK105, 0.2 part of dispersant B YK163, 0.05 part of defoamer TEGOfoamexK3, 2.5 parts of calcium hydroxide, 0.4 portion of antifreeze, 10 parts of Pulvis Talci, 5 parts of Kaolin, 10 parts of iron oxide yellows are added sequentially in reaction vessel, often add a kind of raw material, after stirring, add another raw material, high speed dispersion 1.5h under room temperature, both organic silicon modified polyurethane water-repellent paint can have been obtained after stirring。
Embodiment 5
(1) according to weight ratio, by 100 parts of monohydroxy polydimethylsiloxane, 15 parts of toluene di-isocyanate(TDI)s, 5 parts of hexamethylene diisocyanates, 15 parts of isophorone diisocyanate join reacts 5h under the catalytic action of dibutyl tin dilaurate at 70 DEG C in reaction vessel, then add 40 parts of trimethylolpropanes, continue reaction 2.5h, prepare the chain extender containing organosilicon long-chain。
(2) according to weight ratio, in the reactor equipped with stirring and temperature regulating device, it is sequentially added into 100 parts of PTMG dihydroxylic alcohols, 50 parts of isophorone diisocyanate monomers react 6h at 100 DEG C, it is subsequently adding 13 parts of chain extenders prepared in (1) at 70 DEG C, reacts 3.5h, namely can obtain organic silicon modified polyurethane prepolymer product。
(3) according to weight ratio, by 100 parts of organic silicon modified polyurethane prepolymers, 15 parts of dioctyl phthalates, 3 parts of dibutyl phthalates, 0.1 part of wetting agent K-LS315, 0.4 part of wetting agent BYK346, 0.2 part of dispersant B YK163, 3 parts of calcium oxide, 0.5 part of calcium hydroxide, 0.05 part of antifreeze ethanol, 0.15 part of antifreeze methanol, 5 parts of zinc oxide, 5 parts of iron oxide reds are added sequentially in reaction vessel, often add a kind of raw material, after stirring, add another raw material, high speed dispersion 2h under room temperature, both organic silicon modified polyurethane water-repellent paint can have been obtained after stirring。
Organic silicon modified polyurethane water-repellent paint prepared by embodiment 1～5 is tested according to the performance requirement of GB/T16777-2008 " polyurethane water-proof paint ", and the performance detected is as shown in Tables 1 and 2。
Wherein, the saturated Ca of alkali treatment conditions: 0.1%NaOH+ (OH)2Solution, 168h；Acid reaction variables: 2%H2SO4Solution, 168h。
The performance of table 1 organic silicon modified polyurethane water-repellent paint
Note: B2-E: igniting 15s, burn 20s, Fs 150mm, ignites filter paper without density flaming droplet。
The contact angle of table 2 organic silicon modified polyurethane water-repellent paint
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Contact angle/0 | 103 | 98 | 95 | 93 | 100 |
Be can be seen that by the data of table 1 and table 2, the performance of the single-component organic silicon modified polyurethane water-repellent paint prepared by the present invention disclosure satisfy that the Essential Performance Requirements of GB/T16777-2008 " polyurethane water-proof paint ", contact angle and ageing-resistant realize organic silicon polyurethane water-repellent paint prepared by the data display present invention and there is the ageing-resistant performance of excellence and long-term water-fast, the performance such as antifouling。
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention。
Claims (10)
1. a mono component wet solidifying organic silicon modified polyurethane water-repellent paint, it is characterised in that specifically include the following component according to weight portion:
The preparation method of described organic silicon modified polyurethane prepolymer is as follows: according to weight ratio, (1) by 100 parts of monohydroxy polydimethylsiloxane, 5～30 parts of diisocyanate are blended under catalyst action at 50～100 DEG C and react 0.5～5h, add 10～40 parts of trimethylolpropanes, continue reaction 1～3h, prepare the chain extender containing organosilicon long-chain；(2) by 50～100 parts of PEPA/polyether polyol, 5～50 parts of isocyanate-monomers react 5～10h at 50～100 DEG C, add the chain extender that 5～25 parts of steps (1) prepare at 50～100 DEG C, react 3～5h, namely can obtain organic silicon modified polyurethane prepolymer。
2. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterised in that: the mol ratio of the isocyanate group that amount is the hydroxyl according to monohydroxy polydimethylsiloxane and diisocyanate of monohydroxy polydimethylsiloxane used and diisocyanate is 1:1。
3. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterized in that: described isocyanates be toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate, 4,4-methyl diphenylene diisocyanate and 1, at least one in hexamethylene-diisocyanate。
4. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterized in that: described PEPA is average functionality is 2, and at least one in para Toluic Acid's PEPA, toluene PEPA, succinic acid PEPA, polycaprolactone polyol and decanedioic acid PEPA that molecular weight is 1500～6000。
5. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterised in that: described polyether polyol is at least one in Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol and PTMG。
6. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterised in that: described catalyst is organic tin catalyst。
7. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterised in that: described filler is at least one in silicon dioxide, zinc oxide, titanium oxide, Kaolin, Pulvis Talci, mica powder, calcium carbonate and montmorillonite；Described plasticizer is at least one in chlorinated paraffin, o-phthalic acid dibutyl ester and dibutyl phthalate；Described defoamer is at least one in BYK055, BYK066N, BEK760, DF-879, TEGOfoamexK3, calcium oxide, calcium hydroxide and Lithium hydrate。
8. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 1, it is characterised in that: also include 0～10 weight portion pigment, 0～0.5 weight portion levelling agent, 0～0.5 weight portion wetting agent, 0～0.5 parts per weight dispersing agent and 0～0.5 weight portion antifreeze。
9. mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to claim 8, it is characterised in that: described pigment is at least one in the inorganic pigment of Degussa white carbon black, iron oxide red and iron oxide yellow；Described levelling agent is at least one in esters of acrylic acid levelling agent, polydimethylsiloxane class levelling agent and polyether-modified polydimethylsiloxane class levelling agent；Described wetting agent is at least one in TEGO450, BYK346, Silok8040 and K-LS315；Described dispersant is at least one in BYK-P104, BYK-P105 and BYK-163；Described antifreeze is at least one in propylene glycol, ethylene glycol, ethanol and methanol。
10. the preparation method of the mono component wet solidifying organic silicon modified polyurethane water-repellent paint according to any one of claim 1～7, it is characterized in that comprising the steps: 100 weight portion organic silicon modified polyurethane prepolymers, 5～50 parts of filler material by weight, 10～30 parts by weight of plasticizer, 0.5～5 weight portion defoamer mixing, it is uniformly dispersed, obtains mono component wet solidifying organic silicon modified polyurethane water-repellent paint。
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